Sulphuric derivatives of higher alcohols



Serial No. 700,355. 1928 v This invention relates to the preparation of sulphated higher fatty alcohols, and in certain yspecmc embodiments pertains to sodium lauryl I sulphate and sodium 'myristyl sulphate either alone or associated'with other sodium salts of 3' the sulphuric reaction productsof n-straightchain primary alcohols having from 8 to 18 carbon atoms, as new compounds and compositions of matter. This application is a continuation in part of applicant's co'pending applications Serial No. 433,815, filed March 6,1930; Serial No. 650,203, qfiled' January 4, 1933; and Serial No. 614,053, flled'May'27, 1932.

' '15 One object of the invention is to prepare lauryl sulphate and myristyl sulphate, and their salts. Another object is to prepare sulphuric reaction products of mixed alcohols obtainable by the I, f catalytic hydrogenation of higher fatty acid mix- 'tures or their derivatives or substitution products,

for example,fglycerides. In another of its embodiments the invention relates to the catalytic hydrogenation of cocoa- "nut oil and of palm kernel oil to reduce the carboxylic constituents thereof to the corresponding alcohols, the distillation of the reaction products to remove the lower boiling conby means of conventional strong sulphonatlng 6 agents, and the neutralization of the alkyl sulphuric'acid esters so formed to produce salts. A still furtherobject of the invention resides in the application of the novel sulphation products to the cleansing, dispersing, emulsifying and wetappear hereinafter.

' The following examples illustrate various methods of producing the novel productsconstituting the present invention.

9 Example 1 Example 2 One thousand'kilograms of cocoanut oil are introduced intoaan-iron mixing tank together stituents thereof, the sulphation of the residue as ting arts." Other obiec of the inventm Wm- UNITED STATES PATENT oFllCE'I Heinrich Bertsch, Chemnitz, German assignor to American Hyalsol Corporation, Wilmington,

Del., a corporation of Delaware No Drawing. Application November- 20, 1038 In Germany March 80,

12 Claims. (Cl. 280--99J2) with 28 kilograms of the catalyst,'prepared as follows: A copper kieselguhr catalyst is prepared by precipitating copper carbonate onto kiesel-' guhr from an aqueous copperrnitrate solution by means of sodium carbonatepi'ollowed by 111-- tration, washing, drying and pulverizing'of the precipitate. There also is added to the mixing tank, 8 kilograms of copper carbonate prepared by precipitation from the nitrate by-means of sodium carbonate followed by'illtration, washing, drying and pulverlzing.

The mixture of cocoanut oil and catalyst thus produced is stirred'and warmed to about 50 0., hydrogen being introduced into the mixture and maintained at a pressure of the order of 8500 lbs/sq. in. The mixture is further heated, the hydrogenation starting at about 270 0., and the temperature raised to about 340 C. After about 45 minutes, the reduction product is discharged from the reaction vessel, is'cooled and filtered to remove the catalyst. The water layer is then separated from the oil layer, the latter comprising crude lauryl'alcohol' together with other alcohols having from 8 to 18 carbon atoms.

The crude lauryl alcohol may then be vacuum steam distilled under an absolute pressure of about 20 mm. to produce the desired product. A forerun fraction of kilograms per 1000 kilograms from the crude. lauryl alcohol is removed. Distillation starts at about C. and

finishes at about 250 'C. The main cut, (distilled off up to 250 C.,) comprising 850 kilograms per 1000 kilograms of crude lauryl alcohol, consists mainly of lauryl alcohol together with myristyl, cetyl, and stearyl alcohols in smaller amounts; and other' alcohols ranging from 8 to 18 carbon atoms in still smaller quantities.

About 300 kilograms of the'lauryl alcohol fraction obtained as described above is charged into a 1200 liter enameled sulphonator vessel and is cooled to about 33 C. while being stirred. There is then slowly added with stirring 160 kllograms of chlorosulphonlc acid, the acid being added at such a rate that the temperature does not go above 40 C. The acid is addedin portions product is a paste comprising the sodium salts of lauryl and the other alkyl sulphate esters.

To obtain a powder, the paste together with water can be sprayed into a hot air chamber maintained at a temperature of about 100 C. whereby the water is removed and a light iluify powdered product is obtained.

The above examples illustrate the production of mixed alkyl-sulphate esters and their salts.

' If it is not desired to producelmixed sulphate esters, the individual alcohols, for example, lauryl or myristyl, can be sulphated and/or neutralized in the same way. I I

sulphation is eflected by the use of'strong sulphonating agents such as 100% H2804, chlorsulphonic acid or fuming sulphuric acid. The sulphation temperatures may be varied according to the specific alcohol or mixtures of alcohols to be treated, but will ordinarily run from 0 C. to 50 C., the preferred temperature being 30 C. to 40 C. The alcohols will ordinarily be heated up to their melting points before sulphating, although the use of solventsfor the alcohols permits the use of lower temperatures.

The action of the sulphating agents may be assisted by the use of organic or inorganic dehydrating agents, for example, acetic anhydride, phosphorous pentoxide and the like.

The major reaction taking place under the conditions described in the examples is one of sulphation as illustrated in the following equation:

Under certain other conditions, and especially where temperatures above 40 C. are used, a cer: tain amount of sulphonation generally takes place.

The normal straight-chain higher fatty alcohols such as lauryl and myristyl may be readily obtained bythe catalytic hydrogenation of palm kernel or cocoanut oil. However, the source of the alcohol is not material to the broadest concepts of the present invention, except to indicate that the starting materials employed are readily available at a low cost.

The products produced by the reactions described above are true alkyl sulphuric acids, particularly mono esters of sulphuric acid. Normally when these esters are employed in industrial proc-- esses, they are used in the form of their salts produced by neutralizing with any of the various alkalies such as the hydroxides of sodium, potassium, lithium, or with the hydroxides of ammonium, calcium or magnesium. The salts may also be produced by neutralizing the sulphate esters with various metal oxides or with metal salts which will react to give salts of the sulphuric esters, for example, lead acetate.

, The productsobta'ined in accordance with the present invention, consisting principally of true esters or their salts are very stable under ordinary conditions of industrial use. Many of their salts, namely, the. sodium, potassium, lithium, ammonium, magnesium and lead salts, are water-soluble and are of great utility in the various arts. They are valuable agents for wetting and finishing artificial and natural textile fibers, for treating leather, for making pharmaceutical preparations, in the art of working metal, for manufacturing insecticides and dust-binding media, in ceramics, and as a foaming fire extinguishing medium (in which case 5% of sulphate ester salt may be added to a 10% solution of sodium bicarbonate and the solution used in conjunction with sulphuric, acid as a gas liberating agent). The sulphate esters and their salts may furthermore be used wherever moistening,- permeating, emulsiflcation, dispersing, colloidal cleaning, and softening properties are desired. 7

The quantities of materials and reaction conditions set out in the above description and example. may be varied within reasonable limits, and any such variation which is withinv the spirit of the invention is intended to beincluded within the scope of the claims.

I claim:

1. The method of producing agents of the class described, which comprises removing substantially all of the alcohols having a number of carbon a sulphonatlng agent at about the temperature at which the mixture melts, and neutralizing the resulting msas composed principally of the sulphate of lauryl alcohol with a base.

3. A process of producing agents of the class described comprising reducing the carboxylic constituents of a member of the group consisting of cocoanut and palm kernel oil into alcohols, distilling oflf the lower boiling constituents and treating the residual higher boiling alcohol mixture with chlorsulphonic acid added in small portions during constant stirring at about the temperature at which the mixture melts, and neutralizing the :resulting mass composed principally of sulphate of lauryl alcohol with a base.

4. The process of producing agents of the class described, comprising reducing the carboxylic constituents of a member of the group consisting of cocoanut and palmkernel oil, into alcohols, distilling off the lower boiling constituents and sulphonating the residual higher boiling alcohol mixture which comprises essentially lauryl, myristyl, cetyl, and stearyl alcohols.

5. The process of producing agentsof the class described, comprising reducing the carboxyl constituents of'a member of the group consisting of cocoanut and palm kernel oil, into alcohols, producing a fraction comprising essentially lauryl, myristyl, cetyl and stearyl alcohols, by distilling oif about kgs. per 1000 kgs. of original alcohol mixture, and leaving out a residue of about 25 kgs. per 1000 kgs., and sulphonating the said higher boiling alcohol mixture. r

6. The agents of the class described comprising a mixture of sulphonated alcohols consisting essentially of lauryl, myristyl, cetyl and stearyl normal primary alcohols;

7. Water soluble salts of the sulphonated mixture of alcohols described in claim 6.

8. The agents. of the class described comprising principally the sulphate ester of normal primary laiu'yl alcohol, but also containing sulphate esters of myristyl, cetyl, and stearyl normal primary alcohols. 1

9. Water soluble salts of the sulphate ester mix- I ture described in claim 8.

I the steps comprising vacuum steam distilling the alcohol mixture under an absolute pressure of comprising essentially lauryl, myristyl, cetyl and stearyl alcohols, and then sulphating this residual alcohol mixture.

12. Process of producing wetting and finishing agents for the treatment of textile fibers and leather which comprises catalytically hydrogenating palm. kernel oil, thereby producing a mixture of alcohols corresponding to the fatty acids of said oil, distilling said mixture of alcohols to separate out the lower boiling alcohols from said mixture,

then sulphonating the remaining alcohols and neutralizing them to form water soluble salts.

HEINRICH BERTSCH. 

